Process for manufacturing cast iron and other materials



July 26, 1938. c. BRATASIA'NU PROCESS FOR MANUFACTURING CAST IRON AND OTHER MATERIALS Filed ,June 11, 1934 5 Sheets-Sheet 1 II I July 26, 1938.- c. P. BRATASIANU. I 3 9 PROCESS FOR MANUFACTURING CAST IRON AND OTHER MATERIALS Filed June 11, 1954 5 Sheets-Sheet 2 0'. Efrain-W,

July 26, 1938. c. P. BRATASIANU ,9

PROCESS FOR MANUFACTURING CAST IRON AND OTHER MATERIALS I Filed June 11, 1934 ssneets-sheei s July 26, 1938. c. P. BRATASIANU 2,124,905

PROCESS FOR MANUFACTURING QAST IRON AND OTHER MATERIALS FiledJune 11, 1934 s Sheets-Shet 4 GJZBrat'mra'am:

Inflamm- July 26, 1938. c. P. BRATASIANU 2,124,905

PROCESS FOR MANUFACTURING CAST IRON AND OTHER MATERIALS Filed June 11, 1934 5 Sheets-Sheet 5 Fig.5.

Patented July 26, 1938 PROCESS FOR AND PATENT OFFlCE MANUFACTURING CAST IRON OTHER MATERIALS Constantin Paul Bratasianu, Craiova, Rumania Application June 11, 1934, Serial No."zao,os1

In Bumania June 13, 1933 9 Claims.

This invention relates to a process for treating simultaneously and together, by chemical and metallurgical meansfsplid combustible materials of poor quality to improve them, heavy hydrocarbons to convert them into light hydrocarbons, and iron ores to carburize them, and for then treating these improved products in a metallurgical furnace for the purpose of obtain ing synthetic cast iron, that is to say cast iron 10 having a low and controllable carbon content or special steels ultimately rich in manganese, aluminium, silicon, etc. in a single fusion opera-g of tars, are converted into light hydrocarbons having a low boiling point by depolymerization or by cracking by processes consisting in heating them at temperatures and pressures frequently of a very high order, and sometimes in the pres-' ence of catalysts. The known processes have the disadvantages, however, that the light products produced often contain phenols, that their yield is reduced, and that they produce large quantities of coke of poor quality or of minimum value. I

value, that is to say, a metallurgical coke, can

. only be obtained from a combustible material of good quality which contains only a certain definite amount of gas, no sulphur, and only a little mineral material which is converted into ash.

The process according to the present invention provides the possibility of manufacturing cast iron or steel directly in two chemical and metallurgical operations, which are carried out in several stages in a series of suitable apparatus, starting with poor pulverulent ores, even containing sulphur, combustible materials which have up to the present not been convertible into coke, and heavy hydrocarbons such as the residues from the distillation of raw petroleum or from distillation of other combustible materials. It will be understood that the process may be varied to suit varying circumstances or requirements-either as to the amount, or the properties of one'or other of the products, and that it may It is known, moreover, that a coke 01 high be interrupted after one or other of the stages, taking an intermediate product as a final product, such as metallurgical coke or a light hydrocarbon capable of use in internal combustion engines or a purified, enriched or carburized ore. The total amount of solid materials present is not less than halfthat of the liquid hydrocarbons.

In accordance with the principal feature of the invention the process for the production of improved cast iron, or steel, and/or for the production of improved intermediate products is characterized by the fact that firstly, iron ores, solid carbonaceous and distillable combustible materials andheavy hydrocarbons (which may all be of poor quality) are subjected to heat treatment at a relatively low temperature (of the order of 500 0.), whereby there are produced high quality metallurgical coke, light hydrocarbons, and purified and carburized ore, and, secondly, said intermediate products (high quality coke, hydrocarbons and ore), so produced, are, if desired, subjected to heat treatment in a fusion furnace at relatively high temperature (of the order of 2000" c.) with the addition, if required, of fluxing materials, whereby there are produced in a single'iusion operation, synthetic pig iron or special steels.

Also in accordance with the invention a special furnace,-hereinafter fully described, is used for carrying out said process. The invention is also concerned with the improved products produced by the said process.

To carry out the process, there may be used:

A solid, poor quality combustible material, such as wood, lignite, coal non-convertible into coke, and even containing sulphur.

An iron ore, fragmentary or pulverized, cone taining oxides of iron, manganese, chromium, silicon (MnO, MliOz, S102) and even an ore containing sulphur.

A residue from the distillation of petroleum, even a parafilnous residue, or a tar.

All these starting materials, taken in proportional amounts depending on their characteristics, and those of the products to be produced,

are introduced together at atmospheric pressure in a. retort subject to heating from outside. It is to be noted that the first operation is to be carried out at a relatively low temperature, about 500 C., and that. the iron oxide and the ores which take part in the reaction serve simultaneously as catalysts, which is the reason why the reactions can be effected at such low temperature.

The interactions which take place simultaneously between the starting materials and between the products of their distillation or their cracking during the operation, these products being in a nascent condition and in the presence of a catalyst, are very complex and cannot yet be fully explained, but having regard to the practical results achieved, it is thought that they are, shortly, as follows:-

(a) the water contained in the combustible material and the ore is dissociated to produce oxygen (0) and hydrogen (H);

(b) the combustible material distils, and gives off tars, hydrogen (H) and methane (CH4), whilst a part of its carbon combines with a part of the oxygen obtained under (a) to form carbon monoxide (C+O=CO);

(c) the ore, upon contact with the carbon monoxide formed under (b) is subjected to reduction and carburization giving rise to the formation of carbon dioxide (FeO+CO=COz+Fe) which, by a reversible reaction, combines with the carbon of, the combustible material (C02+C=2CO)', whilst the ore is carburized on contact with the free carbon set free in the mineral; on the other hand, the catalytic action of the carbon monoxide in the presence of water vapour gives rise to the formation of hydrogen which serves, in conjunction with the hydrogen resulting from the dissociation of the water under (a), to hydrogenize the distillation products of the hydrocarbons or tars introduced into the reaction; I

(d) the hydrocarbons (residues or tars) introduced commence by being decarburized by the available oxygen arising from the water vapour given up by the ore and combustible material,

, From this there results either a gas, or colloidal sulphur which passes into the waste (pitch, ashes, etc.).

This first operation of the process. thus gives:

1. Metallurgical coke, i. e. an enriched combustible material obtained from a poorer quality combustible, which may even be pulverized, the calorific power of which is increased by the carbon from the conversion of the residue or of the tars, which carbon is at the same time a binder.

2. Ore already agglomerated and carburized, without commencing to melt, in the same manher as the combustible material, which ore being already carburized, that is to say, already containing carbon, can be more easily cast than the ore which is usually introduced into the blast furnace and where it was first carburized by con tact with the incandescent coke.

3. Light hydrocarbons rich in aromatics, which arise from the tars, and also in isoparafllns and olefines.

The next step of the present process is carried out in the fusion furnace described below, into which the products already obtained (1. e. the coke, the ore, and the hydrocarbons in the proportions necessary to obtain the desired result) are introduced.

' Example To carry out the first operation of the process there were used:--

150 kilograms of residues from the distillation of petrol (mazout).

50 kilograms of pulverized iron ore containing manganese and a little sulphur.

100 kilograms of wood having a calorific power or 2500 to 3000 calories per kilogram.

The yield was as follows:-

(a) 45 kilograms of carburized ore, agglomerated and sulphur-free;

(b) 48 kilograms of agglomerated metallurgical coke having a calorific power of about 8000 calories per kilogram;

(c) '150 kilograms of light hydrocarbons, which when submitted to ofllcial analyses showed that: v

the fraction of this hydrocarbon which distils up to 95 C. is 34.07% and up to 200 C. is 89.5% of the total amount; the fractions which distil up to 150 C. contain no phenol, those which distil between 150 and 200 C. contain 1.76% of phenols and the, heavier fractions contain 3.10% of phenol.

There are thus obtained from 100 kilograms of solid combustible material having 2500 to 3000 calories per kilogram, 48 kilograms (i. e. 48%) of metallurgical coke having 8000 calories per kilogram, this being a combustible product of which the total calorific content is greater than that 01' the starting material, whilst with other processes there would have been obtained approximately only 30% of wood charcoal having 7000 calories per kilogram.

It is to be pointed out that in other similar experiments carried out in accordance with this process, with lignite, of which the calorific power was about 3500 calories per kilogram there was obtained a quantity or -70% or metallurgical coke having 7700 calories per kilogram and sulphur-i'ree.

Since the results of experiments (including amongst them the example given) prove that the total amount of coke obtained contains more calories than the amount of wood introduced, it must be admitted that this result can only be attributed to the fact that-the derived products rich in aliphatic carbon, in the form of vapour, resulting from the heavy hydrocarbons introduced in the reaction become attached to the combustible material by an action similar to cementation or by a reciprocal penetration which takes place between the solid combustible material (which distils) and the heavy hydrocarbons which undergo dissociation. The combustible material which distils, is first freed oi the light gases such as hydrogen (H) and methane (CI-I4) which difluse amongst the heavy hydrocarbons, whilst the aliphatic carbon which results from the conversion penetrates in the form or carbon monoxide. (CO) into the combustible material,

where it becomes converted in accordance with v the equation ,to benoted that by controlling the reaction judiciously almost 100% may be obtained.

The results of experiment thus show another particular advantage of the new process, namely, that the distillation products arising from carbonization at low temperature of carboniferous materials become mixed, immediately they are formed, with the hydrocarbons which have been introduced, and it is in combination with the latter that they are submitted to cracking, in such a way that the yield of light products is greater than would be obtained by submitting to the cracking operation only the hydrocarbons introduced.

The result of experiment shows, as in the example given, that the process according tothe invention gives, by the conversion of heavy hydrocarbons, other light ones, which distil between 150 and 200 C. and which are free from phenol, whilst the light hydrocarbons obtained by other processes contain up to 40-50% of phenol. In the new process-the essential fact is that the tars from thesolid carbonaceous material and the heavy liquid hydrocarbons undergo cracking together in the presence of hydrogen. This hydrogen results from the dissociation of water vapour, which water was contained in the solid combustible and the ore, and hydrogen from the reactions themselves as is evolved during the distillation in the presence of catalysts. These catalysts are the ore (preferably rich in manganese, such as MnO and M1102), the carbon (C) and the carbon monoxide (CO), which 5 in a medium rich in hydrogen gives rise to reactions which free the water and methane (C+6H=CH4+H2O) On the other hand the distillation of the solid carbonaceous material gives rise to methyl alcohol (CHaOH). Due to the catalysts the hydroxyl (OH) is broken away and having the methyl radicle (CH3) which prevents the formation of phenol and which, being unstable, combines to form ethane in accordance with the equation CH3+CH3=C2He, which latter, losing successively its hydrogen, changes to ethylene (C2H4) and finally acetylene, (CzHz), which by polymerization changes tobenzene (CsHc) Thus by synthesis an entire light hydrocarbon series is obtained capable of being used in all types of motors.

The enriched products obtained in the first operation of theprocess (i. e. the carburized agglomerated sulphur-free ore, the metallurgical coke, also sulphur-free, as well as the light hydrocarbons free from sulphur, phenols or other oxygen compounds-if it is not intended to use them as such-are then treated in a second 013-, eration for the finishing of the process, that is, for making in a single fusion operation synthetic pigs org special steels. To this end the enriched products are introduced into a suitable furnace, preferably into the special furnace which is one feature of the invention and which is described hereinafter. Besides these products there are introduced fluxes, additions of ores rich in manganese to regulate oxidation andto eliminate eventual traces of sulphur in the combustible material or the ore. iron waste or scrap.

This special fumac'e is a shaft furnace the total height of which need not exceed '7 to 8 metres. It has a lining which, at the high temperature at which it works (about 2000* C.) produces slag similar to cement, from which flag-- stones, tiles, etc. may be made. b

One embodiment of the furnace referred to is shown by way of example in the attached drawings, in which: a

Fig. 1 is a verticallongitudinal section through the furnace and its accessory fittings;

Fig. 2 is a' horizontal section along line 2--2 of Fig. 1, also of'the furnace and its accessory fittings;

Fig. 3 is a vertical transverse section along line 33 of Fig. 2 of the whole installation;

Fig. 4 is a section similar to that of Fig. 3 but showing the furnace proper to a. greater scale;

Fig. 5 is a section similar to that of Fig. 1, showing the furnace alone to a greater scale;

Fig. 6 is a section similar to that of Fig. 2 showing only the absorption chamber of the furnace to a greater scale;

Fig. 7 is a horizontal section along line 'll in Fig.5;- I

Fig. 8 is a horizontal section along line 8-8 in Fi 5.

The furnace functions at very high temperature reaching near 2000 C. produced by the injection of the hydrocarbons referred to and hot air which thus even permits reduction of the There may also be added of combustible liquid in relation to the amount of hot air supplied so that carbon dioxide (CO2) is freed.

gases leaving the furnace, collected in a circular conduit D (Figs. 4 and 5) and sent by a conduit G into alternative recuperator heaters situated adjacent the furnace, fitted with baflies N (Fig. 1) these gases being ignited by the heaters H. The hot air. driven by suitable ventilator means, passes through tubes I and K into circular conduits E and F surrounding the zones, and penetrates by tuyeres S, spaced around the zones, into the latter.

I The combustible liquid in a reservoir V (Fig which takes part in the reactions and gives rise 1) being the light hydrocarbons free from sulphur, btained in the first stage situated in a hot place of the furnace, is distributed by piping Q and R and is introduced into the furnace by the same hot air tuyres already mentioned.

The furnace s cooled by means of water from a reservoir W, passing through a system of pipes situated in the actual masonry of the furnace,

and provided with valves necessary to cause circulation of the water into the overheated parts, indicated by an escape of steam-the purpose of which is to draw attention to the fact that the injection of combustible material on the side of the furnace opposite the overheated part should be reduced.

The furnace is provided with an interior lining to the production of abundant-slag which flows continuously to the furnace chamber. They are collected in trough X filled with water and may be used as an agglomerant having the nature of cement.

. It will be understood that the process may also serve for the treatment of manganese, chromium,

liquid hydrocarbons or tars, to a heat treatment at a temperature not greater than 500 0., to produce purified, agglomerated, carburized and partially reduced ore, high quality metallurgical coke and light liquid hydrocarbons, and subjecting said three products in a second stage, to heat treatment at temperatures ranging from 1000. to 2000 C., for the production, in a single fusion operation, of cast-iron or steel.

2. A two stage process for the production of cast-iron or steel, comprising subjecting in the first stage iron ores, solid carbonaceous, distillable combustible materials and heavy liquidhydrocarbons, all of which may contain sulphur,

[together to heat treatment, at atmospheric pressure in a retort at a temperature not greater than 500 C. and subjecting the three products so obtained in a second stage to a second heat treatment in a shaft furnace at a temperature between 1000 and 2000 C., for the production in a single fusion operation of' cast-iron or steel.

3. In a two stage process for the production of cast-iron or steel, the step of producing charging products by subjecting together iron ores, solid carbonaceous combustible material -and heavy hydrocarbons to heat treatment at relatively low temperature, to distil the-combustible materials, to crackthe hydrocarbons and to reduce the ores, whereby there are obtained respectively agglomerated, carburized and partially reduced ore, metallurgical coke and synthetic light liquid hydrocarbons, the step of admitting said ores and coke mixed with common fluxing agents, manganese ores and iron scrap to the heating chamber of a shaft furnace and subjecting said mixture to temperatures between 1000 and 2000 0., obtained by injecting said light hydrocarbons and hot air in controllable proportions.

4. In a two stage process for the production of cast-iron or steel, the step of producing charging products by subjecting together iron ores, solid carbonaceous combustible material and heavy hydrocarbons to heat treatment at relatively low temperature to distill the combustible materials, to crack the hydrocarbons and to reduce the ores, whereby there are obtained respectively agglomerated, carburized and partially reduced ore, metallurgical coke and synthetic light liquid hydrocarbons, admitting said ores and coke mixed with common fluxing agents, manganese ores and iron scrap, to the heating chamber of a shaft furnace,-heating the upper zone of said furnace to a temperature of about 1000 C. by the injection of hot air and liquid hydrocarbons in controllable proportions to obtain a reducing zone and heating the lower zone of said furnace also by injecting hot air and liquid hydrocarbons in controllable proportions to obtain an oxidizing and melting zone at a temperature of about 2000 C. whereby there is obtained cast-iron or steel as required.

5. A two-stage process for the production of cast-iron or steel, comprising subjecting in the first stage crude iron ores, crude solid carbonaceous distillable combustible materials, such as wood, lignite, coal and the like and heavy liquid hydrocarbon residues or tars, together to a heat treatment at a temperature not greater than 500 0., to produce purified, agglomerated, carburized and'partially reduced ore, high quality metallurgical coke and light liquid hydrocarbons, and subjecting said three products in a second stage, to heat treatment at temperatures ranging from 1000 to 2000 C., for the production, in a single fusion operation, of cast-iron or steel.

6. A two-stage process for the production of cast-iron or steel, comprising subjecting in the first stage crude iron ores containing manganese, crude solid carbonaceous distillable combustible materials, and heavy liquid hydrocarbons, all of which may contain sulphur, together to heat treatment, at atmospheric pressure in a retort at a temperature not greater than 500 C. and subjecting the three products so obtained in a second stage to a second heat treatment in a shaft furnace at a temperature between 1000 and 2000 0., for the production in a single fusion operation of cast-iron or steel.

7. Ina two-stage process for the production of cast-iron or steel the step of producing charging products by subjecting ogether iron ores,

solid carbonaceous combus'ble material and heavy hydrocarbons to heat treatment at relatively low temperature to distil the combustible materials, crack the hydrocarbons and reduce the ores for the production respectively of agglomerated carburized and partially reduced ore, metallurgical coke and synthetic light liquid hydrocarbons; admitting said ores'and coke in a second stage mixed with common fluxing agents, manganese ores and iron scrap to the heating chamber of a shaft furnace, subjecting said mixture to a temperature between 1000 and 2000 C. obtained by injecting said light hydrocarbons and hot air in controllable proportions to produce cast-iron or steel and admitting the molten cast-iron or steel and slag to a reaction chamber adjacent said furnace at the base thereof and heated by gases from the lower zone I of the furnace, adding in. said chamber during operation powdered substances for the removal of the last traces of sulphur and other materials according to the kind'of cast-iron or steel required. V

8. In a two-stage process for the production of cast-iron or steel the step of producing charging products by subjecting together iron ores, solid carbonaceous combustible material and heavyhydrocarbons to heat treatment at relatively low temperature to distil the combustible materials, crack the hydrocarbons and reduce the ores for the production respectively of agglomerated carburized and partially reduced ore, metallurgical coke and synthetic light liquid hydrocarbons; admitting said ores and-coke in a second stage mixed with common fluxing agents, manganese ores and iron scrap to the heating chamber of a shaft furnace, subjecting said mix ture to a temperature between 1000' and 2000 0. obtained by injecting said light hydrocarbons and hot air in controllable proportions to pro duce cast-iron or steel and adding during operation powdered substances for regulating oxidation, according to the kind of cast-iron or steel required. I y

9. In a two stage process for the production of cast-iron or steel the step of producing charging products by subjecting together iron ores, solid carbonaceous combustible material and heavy hydrocarbons to heat treatment at relatively low temperature to distll the combustible material, crack the hydrocarbons and reduce the ores for the production respectively of agglomerated, carburized, and partially reduced ores. metallurgical coke, and synthetic light liquid hydrocarbons, admitting said ores and coke mixed with common fluxing agents, manganese ores and iron scrap to the heating chamber of a shaft furnace having a thick lining, subjecting said mixture to temperatures between 1000 and 2000 C. obtained by injecting said light liquid hydrocarbons with hot air in controllable proportions, admitting the molten cast-iron or steel and slag to a reaction chamber adjacent said shaft furnace and at the base thereof and heated by gases from the lower zone of ,the furnace, adding in said chamber during operation powdered substances for the removal of the last traces of sulphur and other materials according to the kind of cast-iron or steel required, said additions being retained in the reaction chamber by the pressure of said gases, providing a system of conduits located in the masonry of the furnace through which water is circulated in controllable amounts to regulate the temperature of the masonry and of the lining of the furnace CONSTANTIN PAUL BRATASIANU. 

